US2171166A - Condensation product from p-di-chlorbenzol and sulphuric anhydride and its derivatives - Google Patents

Description

was Aug-29. 9 9 2,111,166

u rrEo STATES PATENT OFFICE CONDEI iSATION PRODUCT FROM P-DI- CHLOBBENZOL AND SULPHUR-1C ANHY- DBIDE AND ITS DERIVATIVES will! SO01, Milan, Italy I No Drawing. Application February 27, 1935, Se- 1 rial No. 8,506. In Germany March 2, 1934 a claims- (c1. zoo-45v) This invention relates to novel organic comquantitatively to form one moi of H2804 and 2 pounds and to processes for preparing the samemols of para-dichlorbenzene sulphonic acid by More particularly, this invention deals with novel adding 2 mols of water. Furthermore, this prodcompounds obtained by treatment of dichlorouct, contrary to all expectation, readily forms con- 5 benzenes with sulphuric anhydride, and with furdensation products in which the sulphate-radical ther compounds obtainable by condensing the is replaced by an inorganic or organic group, by aforesaid novel compounds with organic or inorsplitting of! sulphuric acid. These condensation ganic compounds having a readily exchangeable products are suitable for many and varied 178011111? hydrogen atom. cal uses. According to the choice of the com- It is an object of this invention to produce novel pound used for the condensation, products are :1!

7 organic compounds which are useful in the variobtained which are useful as insecticides, textile ous technical arts such as the treatment of textile assistants, or dye intermediates. fibers, pest control, and manufacture and appli- The special conditions above referred to concation of dyestufls. It is a further object of this slst of using a relatively concentrated sulphonatinvention to provide a novel process for inducing ing agent while avoiding elevated temperatures. 15 a reaction between dichlorobenzene and sulphuric Oleum of at least 10% strength should be used as anhydride whereby to produce novel compounds. the sulphonating agent. Best results are ob- Other and further important objects of this tained with 30% oleum, but higher concentrations invention will appear as the description proceeds. 31p to the strongest commercial grades are appli- .20 It has been believed in the art that p-dichlorocable. The temperature during sulphonation benzene is incapable of sulphonatlon except under should be kept below 100 C. Best results are very stringent conditions, and even then but very obtained at room temperature or lower. poorly. (Beilstein, 3d. ed., Vol. 11, page 119, para- 01 the materials capable of condensing with my graph 2; Zeltsch. fiir Chemie, 1868, vol. 4, page novel reaction product may be mentioned the 226; Monatshefte der Chemie, 1927, vol. 48, page organic amines, amides, imines, alcohols, mercap- 25 627.) tans, phenols, carboxylic acids, aldehydes, sul- I have now found that when para-dichlorbenphonic acids, sulphinlc acids, sulphamides and zone is treated under certain conditions with the various salts of these, and also inorganic hyoleum, as more fully set forth below, it forms a droxy compounds such as arsenious acid, arsenic homogeneous condensation product consisting of acid, the corresponding acids of phosphorus, anti- 3 mols of S03 and 2 mols of para-dichlorbenzene mony, bismuth, and nitrogen; salts of these; amwith the loss of one molecule of water. The prodmonia and its derivatives; derivatives of cyanouct thus obtained appears to have the following gen, etc. In condensations of this type the radiconstitution cal S04 appears to be eliminated and two radicals O Y of the organic or inorganic compound seem to take its place, as is illustrated by the following equation which is believed to represent the reaction between bis-(2,5 dichlorobenzene 4 sul- :i i: phonic-acid-anhydride) -su1phone and aniline.

"" 0 0 i CIHI and may be designated bis-(2,5-dichlorobenzenerm NB 4-sulphonic acid anhydride') -su1phone. O 0 0 7 0 l L 0 Products of this type have not as yet been de- \5 1% I R-----S-R+4 R- scribed in the literature. It is true that certain 5 organic compounds on sulphonation give intermediate products to which the SO: radical is attached; these are, however, unstable. The above produchhowever, is so stable that it can be T e fi fl e Sulphone a d its c densation so readily isolated, washed and dried. Contrary to prod cts as a ve describe are useful for various the known p-dichlorbenzol-sulphonic acid the new P p Such as insecticides. u g cides. assistproduct of bis-(2,5-dichlorobenzene-4-su1phonicants in the treatment of textile material, oxidizing acid-anhydride)-sulphone is insoluble in water. agents for use in printing with vat dyestuffs, It decomposes only after several hours heating in intermediates for the manufacture of various dyethe presence of water, whereupon it breaks up stufls, etc.

-As insecticides, my novel products are particularly useful for moth-proofing textile fabric, especially wool. Here, they have the advantage of not being volatile; hence neither weakening with age nor spreading poisonous fumes. Furthermore, they do not wash out readily from the fiber. They are, however, inert with respect to other operations to which the textile material may be subjected and therefore do not interfere with such. 1 7

My nu'vel products are also useful as intermediate for colors of the Supramine as well as Thioindigoid types. They are capable of chang-' ing the shade of azo dyestuffs, and remarkably increase the fastness to light and washing as well as the purity of the shade obtained by dyeing with such colors.

The anhydride-sulphone is also advantageously used as an oxidizing agent in the printing of wool with vat dyestufis, and'they have'the advantage over persulphates or acids in that they give oir H2804 but slowly.

melts at 108 1155? C.

Without limiting my invention to any particular procedure, the following examples are given to illustrate my preferred embodiments thereof. Parts mentioned are by weight.

Ewample 1 50 parts of para-dichlorbenzene are added to v m 26 parts of the product obtained according to Example 1 are heated for 2 to 3 hours at 95 C. with 14 parts of the sodium salt of benzol sulphinic 200parts of 30% oleum at a temperature of about 15 C. The temperature is raised with good agitation to about 25 C., which'temperature is-maintained for 10 hours. then pouredintoa mixture of 200'partsof water and 300 parts of ice and the product which separates is filtered on, washed until neutral, and

dried. It is in the form of a white powder which The amount and strength 7 of the oleum can bevaried within wide-limits. The same is true of the temperature. Also moly ten para-dichlorbenzene can be added to the oleum or the oleum may be added'to molten paradichlorbenzene; if desired,'the para-dichlorbenzene can be added in solution orin the presence of diluents, or the oleum may be added tosuch; solutions or dilutions of para-dichlorbenzene. If desired, free sulphuric "acid used in place of oleum. 11

The product thus obtained is believed to be bis(2,5- dichlorobenzene 4 i'sulphonio-acidmnhye dride)-sulphone corresponding to the above for mula. Upon boiling in water it decomposes-into.

sulphuric acid and p dichlorobenzene-sulphonic acid. It behaves towardamines in thesame manher as a sulphone chloride; that; is, it condenses to give a sulphonamidetsasindicated by the equa; tion above. When tratediwith reducing agents, according to the methods of reducing -aryl-.-sulphone-chlorides, it yields sulphinicacids and mercaptansi f Analysis of the product gave the following-results:

Computed ior 2CcH4Clg.3SOzH:O. Fmmd Percent Percent 24.91 24.87 13.05 a 18.60 21.24; 27. 32 28.01 27.98 Hydrogen .L 1.17 1.22

The reaction mixture. is

solidi'fiesjaga n at the end of the reaction. partsfof water are added, the mixture is cooled with stirring and the crystallized, colorless prodanhydride may be is heated 6 hours under reflux and after distillation of the toluol is diluted with water and filtered.

After drying, the product is awhite crystalline powder. In place of toluol other solvents may be used, or the condensation may be carried on in a melt without the use of solvents, or in aqueous solution. In place of sodium acetate other salts or acid-binding materials may be used. The aniline may be replaced by other aliphatic and aromatic amines, diamines, hydrazines, sulphamines, sulphamides, or by secondary amines, or by derivatives of the above conlpounds;

Example 3 boxyllc acids, phenols and and their derivatives.

Example 4 acid. The melt becomes fluid for a time but 100 not is filtered off. In place of the sulphinic acid,

v"thiophenols, mercaptans, or their derivatives of thealiphatic or aromatic series may be used.

Example 5 2:6. ofthe product obtained according to Example 1 are added to 200 parts of water and to this are added 35 parts of 1.8.3.8amino-naphthol disulphohic-acid sodium-salt and '13 parts of crystallized sodium acetate. The mix is heated S hours toboiling acidifiedand filtered hot. .2;- acid remains. onlthe filter while the product is in solution. It crystallizes on cooling. In the place of II-acid it is possible to use other amino naphthol-di sulphon acids, am'ino-naphthol monosulphonic, {acid amino-naphthols, naphthylamines, ,naphthalene dia'mines, naphthols, hy-

droxy naphthalenes, andf their derivatives. The

temperature of thefconden'sation reaction and the. amounts of solvents can be varied within wide limits. v 1

Example 6 26 grams of the product obtained according to Example 1 are mixed with a solution which contains 200 grams water, '7 grams of arsenious acid and 13 grams of NaOH (35 Be). The mixture is boiled 10 hours under reflux until every thing is in solution. It is then filtered from the small amount of insoluble residue. and-thefiltrate is cooled. .Thereaction product crys'tahizes in the form of leaflets. Its melting point, is above 250 6; at this temperature it starts to sublime.

In place of arsenious acid it is possible'to use other arsenic derivatives or derivatives 'of phophorus,: antimony, nitrogen, bismuth and cyanogen. Ammoniaand derivatives thereof may likewise be employed. e

It will be understood;that-,my invention is sus- -ceptible of variations and modifications "within wide limits, without departing from the spirit thereof.

Thus, while I preferred in Examples 2 to 6 to carry out the condensation near the boiling point of the mixture, this temperature was employed only as a matter of convenience. For instance, the novel anhydride-sulphone reacts readily with aniline when brought together even in the cold.

Similarly, stoichiometric proportions were employed in some of the examples for the sake of convenience, but, as illustrated in Example 3, this limitation is not absolutely essential.

I claim: l 1. The process of producing a novel organic compound which comprises reacting p-dichlorobenzene with 30% oleum at a temperature be'- tween 15 and C., diluting the reaction mass with cold water and recovering the solid reaction product.

2. The new chemical compound represented by the structural formula I Cl 0 O 0! 3 ap and derivatives thereof in which the S04 radical is replaced by two identical radicals of the group consisting of monovalent substituted lower alkyl, phenyl and naphthyl compounds in which the substituent comprises a member of the group consisting of hydroxy, oxy, amino and sulpho groups.

5. As new chemical compounds, the product represented by the structural formula and derivatives thereof in which the S04 radical is replaced by two identical radicals of an aromatic amine.

6. As new chemical compounds the product represented by the structural formula '1. The new chemical compound represented by the structural formula rie 8. The new chemical compound represented'by the structural formula cr ti s WILLY SEEL.